Reaction products of carboxylated phenol-aldehyde resins and aminemodified phenol-aldehyde resins and process of making same



REACTION PRODUCTS F CARBOXYLATED Pl-ENOLALDEHYDE RESINS AND ANIINE-MODIFlED PHENOL-ALDEHYDE RESINS AND PROCESS OF MAKING SAME Melvin DeGroote, University City, Mo., assignor to Petrolite Corporation,Wilmington, Del., a corporation of Delaware No Drawing. ApplicationOctober 23, 1953 Serial No. 388,051

20 Claims. (Cl. 260-43) The present invention is concerned withprocesses involving reactions between certain amine-modifiedphenolaldehyde resins and certain carboxylated resins. Furthermore, itis concerned with the products so obtained and their uses in variousarts.

U. S. Patent No. 2,571,118, dated October 16, 1951, to De Groote andKeiser, describes a fusible, carboxyl-containing xylene-soluble,water-insoluble, low-stage phenolaldehyde resin; said resin beingderived by reaction between a mixture of a difunctional monohydrichydrocarbon-substituted phenol and salicylic acid on the one hand, andan aldehyde having not over'8 carbon atoms and having one functionalgroup reactive toward both components of the mixture on the other hand;the amount of salicylic acid employed in relation to thenon-carboxylated phenol being suificient to contribute at least onesalicylic acid radical per resin molecule and the amount of difunctionalmonohydric hydrocarbon-substituted phenol being suiiicient to contributeat least one difunctional monohydric hydrocarbon-substituted phenolradical per molecule; said resin being formed in the substantial absenceof phenols of functionality greater than two, and said phenol being ofthe formula in which R is a hydrocarbon radical having at least 4 andnot more than 14 carbon atoms and substituted in one of the positionsortho and para.

More specifically, the present invention is concerned with the reactionbetween said carboxylated resins above described and certainamine-modified thermoplastic phenol-aldehyde resins; such amine-modifiedresins have been described in various patent applications, for example,in co-pe'nding application Serial No. 288,743, filed May 19, 1952, nowU. S. Patent No. 2,718,747 and co-pending application Serial No.376,240, filed August 24, 1953. A typical claim of said firstaforementioned Serial No. 288,- 743, is as follows:

The process of condensing (a) an oxyalkylation-susceptible, fusible,non-oxygenated organic solvent-soluble, water-insoluble, low-stagephenol-aldehyde resin having an average molecular weight correspondingto at least 3 and not over 6 phenolic nuclei per resin molecule; saidresin being difunctional only in regard to methylol forming reactivity;said resin being derived by reactionbetween a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and reactivetoward said phenol; said resin being formed in the substantial absenceof phenols of functionality greater than 2; said phenol being of theformula nited States Patent in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2, 4, 6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a'temperature sufficiently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction; with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the further proviso that theratio of reactants be approximately 1, 2 and 2, respectively; and withthe final proviso that the resinous condensation product resulting fromthe process be heat-stable and oxyalkylation-susceptible.

The carboxylated phenol-aldehyde resins above described generallycontain one or more carboxyl radicals, and generally one or two carboxylradicals. The aminemodified phenol-aldehyde resins above describedinvariably have at least two alkanol radicals and may have more. Thus,the two types of reactants readily can form the equivalent of esters andparticularly linear polymers dependent on ester linkages.

More specifically then the present invention is concerned with anesterification process involving (A) a carbcxylated resin, saidcarboxylated resin being a fusible, carboxyl-containing, xylene-soluble,water-insoluble, lowstage phenol-aldehyde resin; said resin beingderived by reaction between a mixture of a difunctional monohydrichydrocarbon-substituted phenol and salicylic acid onthe one hand, and analdehyde having not over 8 carbon atoms and having one functional groupreactive toward both components of the mixture on the other hand; theamount of salicylic acid employed in relation to the noncarboxylatedphenol being sufiicient to contribute at least one salicylic acidradical per resin molecule and the amount of difunctional monohydrichydrocarbomsub stituted phenol being suificient to contribute at leastone difunctional monohydric hydrocarbon-substituted phenol radical permolecule; said resin being formed in the substantial absence of phenolsof functionality greater-than two, and said phenol being of the formulain which R is a hydrocarbon radical having at least/l and not more than14 carbon atoms and substituted in one of the positions ortho and para;and (B) an amine-modified phenol-aldehyde resin; said amine-modifiedresinvbeing obtainedby the process of condensation of (q)- anoxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weightcorrespending to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional only'in regard to methylol forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of phenols of functionalitygreater than 2; said phenol being of the formula in which R is analiphatic hydrocarbon radical having at least 4 and not more than 24carbon atoms and substituted in the 2, 4, 6 position; (b) a basichydroxylated secondary monoamine having not more than 32 carbon atoms inany group attached to the amino nitrogen atom, and (c) formaldehyde;said condensation reaction being conducted at a temperature sutficientlyhigh to eliminate water and below the pyrolytic point of the reactantsand resultants of reaction; with the proviso that the condensationreaction be conducted so as to produce a significant portion of theresultant in which each of the three reactants have contributed part ofthe ultimate molecule by virtue of a formaldehyde-derived methylenebridge connecting the amino nitrogen atom with a resin molecule; withthe further proviso that the ratio of reactants be approximately 1, 2and 2, respectively; and with the final proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; said esterification reaction being conductedat a temperature sufiiciently high to eliminate water of formation andbelow the pyrolytic point of the reactants and products of reaction.

Furthermore, the present invention is concerned with the productsobtained by the esterification process described immediately preceding.

For purpose of convenience, what is said hereinafter will be dividedinto six parts;

Part 1 is concerned with the preparation of the carboxylated resins;

Part 2 is concerned with the phenol-aldehyde resin which is subjected tomodification by condensation reaction to yield an amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated secondarymonoamines which may be employed in the preparation of theherein-described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the amine, andformaldehyde to produce specific products or compounds;

Part 5 is concerned with the acylation or esterification reactioninvolving the carboxylated resins on the one hand and the amine-modifiedresins on the other hand; and

Part 6 is concerned with uses for the products described in Part 5,preceding.

PART 1 U. S. Patent No. 2,571,118, dated October 16, 1951, to De Grooteand Keiser, describes a fusible, carboxylcontaining, xylene-soluble,water-insoluble, low-stage phenol-aldehyde resin; said resin beingderived by reaction between a mixture of a difunctional monohydrichydrocarbon-substituted phenol and salicylic acid on the one hand, andan aldehyde having not over 8 carbon atoms and having one functionalgroup reactive toward both components of the mixture on the other hand;the amount of salicylic acid employed in relation to thenon-carboxylated phenol being sufiicient to contribute at least onesalicylic acid radical per resin molecule and the amount of difunctionalmonohydric hydrocarbon-substituted phenol being sufiicient to contributeat least one difunctional monohydric hydrocarbon-substituted phenolradical per molecule; said resin being formed in the substantial absenceof phenols of functionality greater than two, and said phenol being ofthe formula:

in which R is a hydrocarbon radical having at least 4 and not more than14 carbon atoms and substituted in one of the positions ortho and para.

The present invention is concerned with the use of suchcarboxyl-containing resins obtained from a reactant mixture in which 1to 2 moles of salicylic acid are used in conjunction with 3 to 5 molesof a substituted phenol as described. In most instances the preferredmixture involves a 3:2 or 4:1 molal ratio of substituted phenol tosalicylic acid.

Assuming one used 4 moles of amylphcnol and one mole of salicylic acid,the resin in its simplest aspect may be represented in an idealized formin the following manner:

on on on on on H a a a n -o OOC O HUB n H Amyl Amy] Aruyl Amyl The aboveformula is, of course, an idealized structure, for obvious reasons,because the salicylic acid nucleus presumably can appear at any point inthe resin molecule. Such resin, or for that matter, a resin having anincreased number of salicylic acid radicals, can be oxyalkylated in thesame manner as other phenol-aldehyde resins.

If obtained from 2 moles of salicylic acid and 3 moles of amylphcnol thecorresponding idealized formula would be thus:

OH OH OH OH OH H H H H HOOG C C -C C OOOH H H H H Amyl Amyl Amy! As tothe preparation of such resins, purely by way of illustration certainexamples are repeated substantially in verbatim form as they appear insaid aforementioned U. S. Patent No. 2,571,118. In said patent there isreference to an example which illustrates resinification without use ofsalicylic acid. For continuity of text this example obviously isincluded.

Example Iaa Grams Para-tertiary butylphenol 150 Formaldehyde, 37% 81Concentrated HCl 1.5

Monoalkyl (C C principally C -C benzene monosulfonic acid sodium salt)0.8 Xylene Examples of alkylaryl acids which serve as catalysts and asemulsifiers particularly in the form of sodium salts, include thefollowing R is an alkyl hydrocarbon radical having 12-14 carbon atoms.

SOsH

R is an alkyl radical having 3-12 carbon atoms and n represents thenumeral 3, 2, or 1, usually 2, in such instances Where R contains lessthan 8 carbon atoms.

With respect to alkylaryl sulfonic acids or the sodium salts, we haveemployed a monoalkylated benzene monosulfonic acid or the sodium saltthereof, wherein the alkyl group contains to 14 carbon atoms. We havefound equally effective and interchangeable the following specificsulfonic acids, or their sodium salts. A mixture of diand tripropylatednaphthalene monosulfonic acid; diamylated naphthalene monosulfonicacids; and nonyl naphthalene monosulfonic acid.

The equipment used was a conventional two-piece laboratory resin pot.The cover part of the equipment had four openings; one for refluxcondenser, one for the stirring device; one for a separatory funnel orother means of adding reactants; and a thermometer well. In themanipulation employed the separatory funnel insert for adding reactantswas not used. The device was equipped with a combination reflux andwater-trap apparatus, so that the single piece of equipment could beused as either a reflux condenser or a water trap, de pending upon theposition of the three-way glass stopcocks. This permitted convenientwithdrawal of water from the water trap. The equipment, furthermore,permitted any setting of the valve without disconnecting the equipment.The resin pot was heated with a glass fibre electrical heaterconstructed to fit snugly around the resin pot. Such heaters, withregulators, are readily available.

The phenol, formaldehyde, acid catalyst, and solvent were combined inthe resin pot, above described. This particular phenol was in the formof a flaked solid. Heat was applied, with gentle stirring, and thetemperature was raised to 80-85 C., at which point a mild exothermicreaction took place. This reaction raised the temperature toapproximately 100-110 C. The reaction mixture was then permitted toreflux at 100l05 C. for between one and one-and-one-half hours. Thereflux trap arrangement was then changed from the reflux position to thenormal water entrapment position. The water of solution and the water ofreaction were permitted to distill out and collect in the trap. As thewater distilled out, the temperature gradually increased toapproximately 150 C. which required between 1.5 to 2 hours. At thispoint the water recovered in the trap, after making allowance for asmall amount of water held up in the solvent, corresponded to theexpected quantity.

The solvent solution so obtained was used as such is subsequentoxyalkylation steps. We have removed also the solvent by conventionalmeans, such as evaporation, distillation, or vacuum distillation, and wecustomarily take a small sample of the solvent solution and evaporatethe solvent to note the characteristics of the solvent-free resin. Theresin obtained in the operation above described was clear, light ambercolored, hard, brittle, and had a melting point of 160165 C. I

Attention is directed to the fact that tertiary butylphenol in presenceof a strong mineral acid as a catalyst and using formaldehyde, sometimesyields a resin which apparently has a very slight amount ofcross-linking. Such resin is similar to the one described above, exceptthat it is sometimes opaque, and its melting point is higher than theone described above and there is a tendency to cure. Such a resingenerally is dispersible in xylene but not soluble to give a clearsolution. Such dispersion can be oxyalkylated in the same manner as theclear resin. If desired, a minor proportion of another and. inertsolvent, such as diethyleneglycol diethylether, may be employed alongwith xylene, to give a clear solution prior to oxyalkylation. This factof solubilization shows the present resin molecules are still quitesmall,

6 both, or an acid such as oxalic acid is used instead of hydrochloricacid. Purely as a matter of convenience due to better solubility inxylene, we prefer to use a clear resin, but if desired, either type maybe employed. (See Example 1a of aforementioned Patent No. 2,571,118.)

Example Zaa Para-tertiary nonylphenol (3.0 moles) grams 660 Salicylicacid (2.0 moles) do 276 Formaldehyde 37% (5.0 moles) do 405 Xylene do700 HCl (concentrated) ml 40 Dodecyl toluene monosulfonic acid sodiumsalt grams 3 Example 3aa Para-tertiary amylphenol (4.0 moles) grams 656Salicylic acid (1.0 mole) cl0 n- 138 Formaldehyde 37% (5.0 moles) do 405Xylene do 700 HCl (concentrated) ml 40 Dodecyl toluene monosulfonic acidsodium salt grams 3 The same procedure was followed as in Example laa,preceding, except that the reflux period was 5 hours, instead of 1 /2hours. Also, note the marked increase in amount of acid used as acatalyst in this instance.

The resin solution so obtained, contained approximately xylene. Thesolvent-free resin was reddish amber in color, slightly opaque,obviously xylene-soluble, and

as contrasted with the very large size of extensively crossducedSlightly, he me 9 reflux:. edusetl:sl sh y r somewhat hard to pliable inconsistency. (See Example 7a of aforementioned Patent 2,571,118.)

Example 4am Para-tertiary amylphenol (3.0 moles) grams 492 Salicylicacid (2.0 moles) do.. 276

Formaldehyde 37% (5.0 moles) do 405 Xylene do 700 HCl (concentrated) ml40 Dodecyl toluene monosulfonic acid sodium salt grams 3 The sameprocedure was followed as in Example laa,

preceding, except that the reflux period was 5 hours, instead of 1 /2hours. Also, note the marked increase in amount of acid used as acatalyst in this instance.

The resin solution so obtained contained approximately 48.8% xylene. Thesolvent-free resin was reddish amber in color, clear, xylene-soluble andsemi-soft or pliable in consistency. (See Example 13a of aforementionedPatent 2,571,118.)

Example 5aa Para-secondary butylphenol (3.0 moles) grams 450 Example 6aaPara-octylphenol (3.0 moles) grams 618 Salicylic acid (2.0 moles) do 276Formaldehyde 37% do 405 Xylene do 700 HCl (concentrated) ml 40 Dodecyltoluene monosulfonic acid sodium salt grams 3 The same procedure wasfollowed as in Example laa,

preceding, except that the reflux period was hours instead of 1 /2hours. Also, note the marked increase in amount of acid used as acatalyst in this instance.

The resin solution, so obtained, contained approximately 42.3% xylene.The solvent-free resin was clear, reddish amber in color,xylene-soluble, and semi-hard to pliable in consistency. (See Example16a of aforementioned Patent 2,571,118.)

Example 70a Grams Para-tertiary amylphenol (4.0 moles) a- 656 Salicylicacid (1.0 mole) 138 Propionaldehyde (5.0 moles) 305 Xylene 700Concentrated sulfuric acid 20 Whenever propionaldehyde or similaraldehydes were employed the procedure was changed slightly from thatemployed in Example laa. The equipment employed, however, was the same.The amylphenol, salicyclic acid, xylene and acid catalyst were combinedin the resin pot, stirred and heated to 150 C. At this point thepropionaldehyde was added slowly for about 1 /2 hours, after which thewhole reaction mass was permitted to reflux for 5 hours at the refluxtemperature of water or slightly above, i. e., l00-110 C., beforedistilling out water. The amount of water distilled out was 102 cc.

The resin solution so obtained contained approximately 41.2% xylene. Thesolvent-free resin was reddish-black, clear, xylene-soluble and hard butnot brittle in consistency.

(See Example 19a of aforementioned U. S. Patent No. 2,571,118.)

PART 2 It is well known that one can readily purchase on the openmarket, or prepare, fusible, organic solvent-soluble, water-insolubleresin polymers of a composition approximated in an idealized form by theformula OH OH OH :Hr: H1:

C C H H R R nR In the above formula n represents a small whole numbervarying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units,particularly when the resin is subjected to heating under a vacuum asdescribed in the literature. A limited sub-genus is in the instance oflow molecular weight polymers where the total number of phenol nucleivaries from 3 to 6, i. e., rz varies from 1 to 4; R represents analiphatic hydrocarbon substituent, generally an alkyl radical havingfrom 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl, ordodecyl radical. Where the divalent bridge radical is shown as beingderived from formaldehyde it may, of course, be derived from any otherreactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it isnecessarily soluble in any organic solvent. This is particularly truewhere the resins are derived from trifunctional phenols as previouslynoted. However, even when obtained from a difunctional phenol, forinstance, paraphenylphenol, one may obtain a resin which is not solublein a nonoxygenated solvent, such as benzone, or xylene, but requires anoxygenated solvent such as a low molal alcohol, dioxane, ordiethyleneglycol diethylether. Sometimes a mixture of the two solvents(oxygenated and nonoxygenated) will serve. See Example 9a of U. S.Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare resins which arexylene or benzene-soluble as described in aforementioned U. S. PatentNo. 2,499,365, or in U. 8. Patent No. 2,499,368, dated March 7, 1950, toDe Groote and Kaiser. In said patent there are describedoxyalkylation-susceptible, fusible, nonoxygenated-organicsolvent-soluble, waterinsoluble, low-stage phenoaldehyde resins havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 carbon atoms and not more than 24 carbonatoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously andreacted approximately one mole of the resin with two moles offormaldehyde and two moles of a basic nonhydroxylated secondary amine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated thus:

The basic hydroxylated amine may be designed thus:

RI HN In conducting reactions of this kind one does not necessarilyobtain a hundred percent yield for obvious reasons.

9 Certain side reactions may take place. For instance, 2 moles of aminemay combine with one mole of the aldehyde, or only one mole of the aminemay combine with the resin molecule, or even to a very slight extent, ifat all, 2 resin units may combine without any amine in the reactionproduct, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehyde or in which R' is the divalent radicalobtained from the particular aldehyde employed to form the resin. Forreasons which are obvious the condensation product obtained appears tobe described best in terms of the method of manufacture.

As previously stated the preparation ofresins, .the kind herein employedas reactants, is well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst such strong acid should be neutralized.Similarly, if a strong base is used as a catalyst it is preferable thatthe base be neutralized although we have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount of a free base. The amount may be as small as at 200th of apercent and as much as a few lOths of a perecnt. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purposes of convenience suitable resins arecharacterized in the following table:

TABLE I M01. wt. Ex- Position R of resin ample R of R derived n moleculenumber 0111 (based on n+2) Phenyl 3. 5 992. 5

Tertiary butyl 3. 5 882. 5 Secondary butyl 3. 5 882. 5 Cyclohexy 3. 51,025. 5 Tertiary amyl 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl.

Propyl 3. 5 805. 5 Tertiary 3. 5 1,036. 5 Octyl 3. 5 1, 190. 5 Nonyl. 3.5 1, 267. 5 Decyl- 3. 5 l, 344. 5 Dodeeyl 3. 5 1, 498. 5 Tertiary butyl.3. 5 945. 5

' Tertiary amyl 3. 5 1,022. 5 N onyl 3. 5 1, 330. 5 Tertiary butyl 3. 51,071. 5

Tertiary arnyl 3. 5 1, 148. 5 Nonyl N 3. 5 1, 456. 5 Tertiary buty] 3. 51,008. 5

Tertiary amyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl 4. 2996. 6

Tertiary arnyl 4. 2 1, 083. 4 Nonyl 4. 2 1,430.6 Tertiary butyl 4. 8 1,094. 4 Tertiary amyL 4. 8 1, 189. G N onyl 4. 8 1, 570. 4 TertiaryamyL 1. 5 604. 0 Cycl0hexyl 1. 5 646 0 H 1. 5 653. 0 1. 5 688. 0

PART 3 As has been pointed out previously the amine herein employed as areactant is a basic hydroxylated secondary monoamine whose compositionis indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicalwhich may beneterocyclic in a few instances as in a secondary aminederived from furfurylamine by reaction as ethylene oxide or propyleneoxide. Furthermore, at least one of the radicals designed by R must haveat least one hydroxyl radical. A large number of secondary amines areavailable and may be suitably employed as reactants for the presentpurpose. Among others, one may employ diethanolamine, methylethanolamine, dipropanolamine and ethylpropanolamine. Other suitablesecondary amines are obtained, of course, by taking any suitable primaryamine, such as an alkylamine, an arylalkylamine, or an alicyclic amine,and treating the amine with one mole of an oxylalkylating agent, such asethylene oxide, propylene oxide, butylene oxide, glycide, ormethylglycide. Suitable primary amines which can be so converted intosecondary amines, include butylamine, amylamine, hexylamine, highermolecular weight amines derived from fatty acids, cyclohexylamine,benzylamine, furfuylamine, etc. In other instances secondary amineswhich have at least one hydroxyl radical can be treated similarly withan oxyalkylating agent, or, for that matter, with an alkylating agentsuch as benzylchloride, esters of chloroacetic acid, alkyl bromides,dimethylsulfate, esters of sulfonic acid, etc., so as to convert theprimary amine into a secondary amine. Among others, such amines include2-amino-1-butanol, 2-amino-2- methyl-l-propanol,2-amino-2-rnetl1yl-1,3-propanediol, 2- amino-2-ethyl-1,3-propanediol,and tri(hydroxymethyl)- aminomethane. Another example of such amines isillustrated by 4-amino-4-methyl-2-pentanol.

Similarly, one can prepare suitable secondary amines which have not onlya hydroxyl group but also one or more divalent oxygen linkages as partof an ether radical. The preparation of such amines or suitablereactants for preparing them has been described in the literature andparticularly in two United States patents, to wit, U. S. Patents Nos.2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August8, 1944, to Spence. The latter patent describes typical haloalkyl etherssuch as CHsOCzHACl (121150 021140 CzHiO CzH4O CzHlCl Such haloalkylethers can be reacted with ammonia or with a primary amine, such asethanolamine, propanolamine, monoglycerylarnine, etc., to produce asecondary amine in which there is not only present a hydroxyl radicalbut a repetitious ether linkage. Compounds can be readily obtained whichare exemplified by the following formulas:

HOCrH;

(CsHi'lO CQ A 21140 CsHi) (CJHQO CHHCH(CH3) 0 (CH3) CHCHz) (C1130CHzGHzO CHQCICIZO CH CHE) (C11 0 UHQCHZCHZ HQ IhC Y) NU ll 0 CzH4 orcomparable compounds having two hydroxylated groups of different lengthsas in (H0 CHnCHnO CHZCHzO CIbCIlz) NH HO CzH| Other examples of suitableamines include alpha-methylbenzylamine and monoethanolarnine; alsoamines obtained by treating cyclohexylmethylamine with one mole of anoxylakylating agent as previously described; beta.-ethylhexyl-butanolamine, diglycerylamine, etc. Another type of amineswhich is of particular interest because it includes a very definitehydrophile group includes sugar amines such as glucamine, galactamineand fructamine,

12 such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, andN-hydroxyethylfruetamine.

Other suitable amines may be illustrated by See, also, correspondinghydroxylated amines which can be obtained from rosin or similar rawmaterials and described in U. S, Patent No. 2,510,063, dated June 6,1950, to Bried. Still other examples are illustrated by treatment ofcertain secondary amines, such as the following, with a mole of anoxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine,phenoxyalphamethyl' amine, phenoxyalphamethylethylamine, andphenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxylgroup and a single basic aminonitrogen atom can be obtained from anysuitable alcohol or the like by reaction with a reagent which containsan epoxide group and a secondary amine group. Such reactants aredescribed, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253,both dated October 16, 1934, to Stallmann. Among the reactants describedin said latter patent are the following:

PART 4 The products obtained by the herein described processes representcogeneric mixtures which are the result of a condensation reaction orreactions. Since the resin molecule cannot be defined satisfactorily byformula, although it may be so illustrated in an idealizedsimplification, it is difiieult to actually depict the final product ofthe cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure hereinemployed is comparable, in a general way, to that which corresponds tosomewhat similar derivatives made either from phenols as differentiatedfrom a resin, or in the manufacture of a phenol-amine-aldehydc resin; orelse from a particularly selected resin and an amine and formaldehyde inthe manner described in Bruson Patent No. 2,031,557 in order to obtain aheatreactive resin. Since the condensation products obtained are notheat-convertible and since manufacture is not restricted to a singlephase system, and since temperatures up to C. or thereabouts may beemployed, it is obvious that the procedure becomes comparatively simple.Indeed, perhaps no description is necessary over and above what has beensaid previously, in light of subsequent examples. However, for purposeof clarity the following details are included.

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind .described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid at the early or low temperature stage of reaction ifemployed as subsequently described; in fact, usually it is apt to be asolid at distinctly higher temperatures, for instance, ordinary roomtemperature. Thus, I have found it convenient to use a solvent andparticularly one which can be removed readily at a comparativelymoderate temperature, for instance, at l50 C. A suitable solvent isusuallybenzene, xylene, or a comparable petroleum hydrocarbon or amixture of such or similar solvents. indeed, resins which are notsoluble except in oxygenated solvents or mixtures containing suchsolvents are not here included as raw materials. The reaction can beconducted in such a way that the initial reaction, and perhaps the bulkof the reaction, takes place in a polyphase system. However, ifdesirable, one can use an oxygenated solvent such as a low-boilingalcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcoholscan be used or one can use a comparatively non-volatile solvent such asdioxane or the diethyl-' ether or ethyleneglycol. One can also use amixture of benzene or xylene and such oxygenated solvent-s. Note thatthe use of such oxygenated solvent is not required in the sense that itis not necessary to use an initial resin which is soluble only in anoxygenated solvent as just noted, and it is not necessary to have asingle phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that inmost cases aqueous formaldehyde is employed, which may be the commercialproduct which is approximately 37%, or it may be diluted down to about30% formaldehyde. However, paraformaldehyde can be used but it is morediflicult perhaps to add a solid material instead of the liquid solutionand, everything else being equal, the latter is apt to be moreeconomical. In any event, water is present as water of reaction. If thesolvent is completely removed at the end of the process, no problem isinvolved if the material is used for any subsequent reaction. However,if the reaction mass is going to be subjected to some further reactionwhere the solvent may be objectionable as in the case of ethyl or hexylalcohol, and if there is to be subsequent oxyalkylation, then,obviously, the alcohols should not be used or else it should be removed.The fact that an oxygenated solvent need not be employed, of course, isan advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether ornot the cogeneric mixture obtained at the end of the reaction is to beused as such or in the salt. form. The cogeneric mixtures obtained areapt to be solids or thick viscous liquids in which there is some changefrom the initial resin itself, particularly if some of the initialsolvent is apt to remain without complete removal. Even if one startswith a resin which is almost water-white in color, the products obtainedare almost invariably a dark red in color or at least a red-amber, orsome color which includes both an amber component and a reddishcomponent. By and large, the melting point is apt to be lower and theproducts may be more sticky and more tacky than the original resinitself. Depending on the resin selected and on the amine selected thecondensation product or reaction mass on a solventfree basis may behard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may bewater-insoluble, or water-dispersible, or water-soluble, or close tobeing water-soluble. Water solubility is enhanced, of course, by makinga solution in the acidified vehicle such as a dilute solution, forinstance, a solution of hydrochloric acid, acetic acid, hydroxyaceticacid, etc. One also may convert the finished product into salts bysimply adding a stoichiometric amount of any selected acid and removingany water present by refluxing with benzene or the like. In fact, theselection of the solvent employed may depend in part whether or not theproduct at the completion of the reaction is to be converted into a saltform.

In the next succeeding paragraph it is pointed out that frequently it isconvenient to eliminate all solvent, using a temperature of not over C.,and employing vacuum, if required. This applies, of course, only tothose circumstances where it is desirable or necessary to remove thesolvent. Petroleum solvents, aromatic solvents, etc., can be used. Theselection of solvent, such as benzene, xylene, or the like, dependsprimarily on cost, i. e., the use of the most economical solvent andalso on three other factors, two of which have been previouslymentioned; (a) is the solvent to remain in the reaction mass withoutremoval (b) is the reaction mass to be subjected to further reaction inwhich the solvent, for instance, an alcohol either low boiling or highboiling, might interfere as in the case of oxyalkylation; and the thirdfactor is this, (0) is an effort to be made to purify the reaction massby the usual procedure as, for example, a water-wash to remove anyunreacted low molal soluble amine, if employed and present afterreaction. Such procedures are well known and, needless to say, certainsolvents are more suitable than others. Everything else being equal, Ihave found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in theearly stage of the reaction because, and for reasons explained, this isnot necessary although it does apply in some other procedures that, in ageneral way, bear some similarity to the present procedure. There is noobjection, of course, to giving the reaction an opportunity to proceedas far as it will at some low temperature, for instance, 30 to 40 butultimately one must employ the higher temperature in order to obtainproducts of the kind herein described. If a lower temperature reactionis used initially the period is not critical, in fact, it may beanything from a few hours up to 24 hours. I have not found any casewhere it was necessary or even desirable to hold the low temperaturestage for more than 24- hours. In fact, I am not convinced there is anyadvantage in holding it at this stage for more than 3 or 4 hours at themost. This, again, is a matter of convenience largely for one reason. Inheating and stirring the reaction mass there is a tendency forformaldehyde to be lost. Thus, if the reaction can be conducted at alower temperature, then the amount of unreacted formaldehyde isdecreased subsequently and makes it easier to prevent any loss. Here,again, this lower temperature is not necessary by virtue of heatconvertibility as previously referred to.

If solvents and reactants are selected so the reactants and products ofreaction are mutually soluble, then agitation is required only to theextent that it helps cooling or helps distribution of the incomingformaldehyde. This mutual solubility is not necessary as previouslypointed out but may be convenient under certain circumstances. On theother hand, if the products are not mutually soluble then agitationshould be more vigorous for the reason that reaction probably takesplace principally at the interfaces and the more vigorous the agitationthe more interfacial area. The general procedure employed is invariablythe same when adding the resin and the selected solvent, such as benzeneor xylene. Refluxing should be long enough to insure that the resinadded, preferably in a powdered form, is completely soluble. However, ifthe resin is prepared as such it may be added in solution form, just aspreparation is described in aforementioned U. S. Patent 2,499,368. Afterthe resin is in complete solution the amine is added and stirred.Depnding on the amine selected, it may or may not be soluble in theresin solution. If it is not soluble in the resin solution it may besoluble in the aqueous formaldehyde solution. If so, the resin then willdissolve in the formaldehyde solution as added, and if not, it is evenpossible that the initial reaction mass could be a three-phase systeminstead of a two-phase system although this would be extremely unusual.This solution, or mechanical mixture, if not completely soluble iscooled to at least the reaction temperature or somewhat below, forexample, 35 C. or slightly lower, provided this initial low temperaturestage is employed. The formaldehyde is then added in a suitable form.For reasons pointed out I prefer to use a solution and whether to use acommercial 37% concentration is simply a matter of choice. In largescale manufacturing there may be some advantage in using a 30% solutionof formaldehyde but apparently this is not true on a small laboratoryscale or pilot plant scale. 30% formaldehyde may tend to decrease anyformaldehyde loss or make it easier to control unreacted formaldehydeloss.

On a large scale if there is any difficulty with formaldehyde losscontrol, one can use a more dilute form of formaldehyde, for instance, a30% solution. The reaction can be conducted in an autoclave and noattempt made to remove water until the reaction is over. Generallyspeaking, such a procedure is much less satisfactory for a number ofreasons. For example, the reaction does not seem to go to completion,foaming takes place, and other mechanical or chemical difficulties areinvolved. I have found no advantage in using solid formaldehyde becauseeven here water of reaction is formed.

Returning again to the preferred method of reaction and particularlyfrom the standpoint of laboratory procedure employing a glass resin pot,when the reaction has proceeded as one can reasonably expect at a lowtemperature, for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or 40 C., for 4 or 5 hours, or at the most, up to -24 hours, I thencomplete the reaction by raising the temperature up to 150 C., orthereabouts as required. The initial low temperature procedure can beeliminated or reduced to merely the shortest period of time which avoidsloss of amine or formaldehyde. At a higher temperature I use aphase-separating trap and subject the mixture to reflux condensationuntil the water of reaction and the water of solution of theformaldehyde is eliminated. I then permit the temperature to rise tosomewhere about 100 C., and generally slightly above 100 C., and below150 C., by eliminating the solvent or part of the solvent so thereaction mass stays within this predetermined range. This period ofheating and re fluxing, after the water is eliminated is continued untilthe reaction mass is homogeneous and then for one to three hours longer.The removal of the solvents is conducted in a conventional manner in thesame way as the removal of solvents in resin manufacture as described inaforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes I have invariablyemployed. approximately one mole of the resin based on the molecularweight of the resin molecule, 2 moles of the secondary amine and 2 molesof formaldehyde. In some instances I have added a trace of caustic as anadded catalyst but have found no particular advantage in this. In othercases I have used a slight excess of formaldehyde and, again, have notfound any particular advantage in this. In other cases I have used aslight excess of amine and, again, have not found any particularadvantage in so doing. Whenever feasible I have checked the completenessof reaction in the usual ways, including the amount of water ofreaction, molecular weight, and particularly in some instances havechecked whether or not the end-product showed surface 16 activity,particularly in a dilute acetic acid solution. The nitrogen contentafter removal of uureacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said asto the actual procedure employed for the preparation of the hereindescribed condensation products. The following example will serve by wayof illustration.

Example I b The phenol-aldehyde resin is the one that has beenidentified previously as Example 2a. it was obtained from apara-tertiary butyl phenol and formaldehyde. The resin was preparedusing an acid catalyst which was completely neutralized at the end ofthe reaction. The molecular weight of the resin was 882.5. Thiscorresponded to an average of about 3 /2 phenolic nuclei, as the valuefor n which excludes the 2 external nuclei, i. c., the resin was largelya mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei,or 5 and 6 overall nuclei. The resin so obtained in a neutral state hada light amber color.

882 grams of the resin identified as 2a preceding were powdered andmixed with 700 grams of xylene. The mixture was refluxed until solutionwas complete. it was then adjusted to approximately 30 to 35 C. and 210grams of diethanolamine added. The mixture was stirred vigorously andformaldehyde added slowly. The formaldehyde used was a 37% solution and160 grams were employed which were added in about 3 hours. The mixturewas stirred vigorously and kept within a temperature range of 30 to 45C. for about 21 hours. At the end of this period of time it wasrefluxed, using a phase-separating trap and a small amount of aqueousdistillate withdrawn from time to time and the presence of unreactcdformaldehyde noted. Any unreacted formaldehyde seemed to disappearwithin approximately 3 hours after the refluxing was started. As soon asthe odor of formaldehyde was no longer detectible the phase-separatingtrap was set so as to eliminate all water of solution and reaction.After the water was eliminated part of the xylene was removed until thetemperature reached about 150 C. The mass was kept at this highertemperature for about 3% hours and reaction stopped. During this timeany additional water, which was probably water of reaction which hadformed, was eliminated by means of the trap. The residual xylene waspermitted to stay in the cogenerie mixture. A small amount of the samplewas heated on a water bath to remove the excess xylene and the residualmaterial was dark red in color and had the consistency of a sticky fluidor a tacky resin. The overall reaction time was a little over 30 hours.n other instances it has varied from approximately 24 to 36 hours. Thetime can be reduced by cutting the low temperature period to about 3 to6 hours.

Note that in T able II following there are a large number of addedexamples illustrating the same procedure. In each case the initialmixture was stirred and held at a fairly low temperature (30 to 40 C.)for a period of several hours. Then refluxing was employed until theodor of formaldehyde disappeared. After the odor of formaldehydedisappeared the phase-separating trap was employed to separate out allthe water, both the solution and condensation. After all the water hadbeen separated enough xylene was ta ten out to have the final productrcflux for several hours somewhere in the range of to C. or thereabouts.Usually the mixture yielded a clear solution by the time the bulk of thewater, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by2.11- examples in Table II.

TABLE II Strength of .Reac- Reac- Max. Ex. Resin Amt., Amine used andamount formalde- Solvent used tion, tlon distill. No. used grs. hydesoln. and amt. tengn, time, temp,

and amt. hrs. 0.

882 Diethanolamine, 210 n 37%, 162 g Xylene, 700 g 32 137 Drethanolamine105 37%, 81 g Xylene, 450 28 150 do Xylene, 600 36 145 30%, 100 rXylene, 400 34 146 .11 Xylene, 450 g 21-23 24 I 141 d Xylene, 600 g21-28 24 145 178 37%, Xylene, 700 g 20-26 24. 152 480 Ethylethanolamine,89 37%, 81 gr... Xylene, 450 "1.-. 24-30 28 151 633 do A r do Xylene,600 gm 22-25 27 147 473 Oycloexylethanolamine, 143 g 30%, 100 g Xylene,450 g. 21-31 31 146 511 .do 37%, 81 g do 22-23 36 148 665 do do Xylene,550 g 20-24 27 152 441 CzHQCzH4O CzH4 X410 Xylene, 400 g.... 21-25 24150 NH, 176 g.

HO C2114 14b 5a 480 CZHEGCZHIQO C2114 d0 Xylene, 450 g. 20-26 26 116 NH,176 g,

HO 02H;

15b- 9a..-" 595 CzHsO CZH4O C2114 do Xylene, 550 g 21-27 30 147 NH, 176g.

16b 2a 441 no C2H4O olnlo 02H, do Xylene, 400 g.... -22 148 NE, 192 g.

HO C 2H4 17b 5a..- 480 HOC2H4OC2H4O C2Hl .do -.do -Q 2025 28 150 NH, 192g.

HO CZHA 18b- 1441.! 511 HOG HrOCgH4OCzHr .do Xylene, 500 g 21-24 32 149NH, 192 g.

H O C2114 19!). 22a 498 HO C2540 C HlO C2H4 ..do Xylene, 450 g. 22-25 32153 NH, 192 g.

HO C2H4 20b- 2311.- 542 CH3(O C2H4)s 30%, 100 g Xylene, 500 g.. 21-23 36151 NH, 206 g.

H O C 2H4 21b. am... 547 cnno 023m do .110 25-30 34 148 NH, 206 g.

H O C2114 22hr 2a.- 441 CHa(O C2114): i -do Xylene, 400 g 22-23 31 146NH, 206 g.

H O 02H;

23b"; 26a. 595 Decylethanolamine, 201 g. Xylene, 500 22-27 24 145 24b-27a 391 Deoylethanolamine, 100 g Xylene, 300 gm. 21-25 26 147 PART 5Needless to say, the two prior reactants can be combined readily bymeans of an acylation reaction and more specifically an esterificationreaction. It has been pointed out previously that the amine-modifiedcondensate must have at least 2 and may have more than 2 alkanolhydroxyl groups. It is to be noted the carboxylated resins may bemonofunctional, difunctional'or even may contain 3 or more .carboXyls.For practical purposes the preferred resin contains one or two carboxylgroups. A .carboxylated resin having one carboxyl group may be reactedwith a suitable amine-modified resin so :as to combine only one suchcarboxylated resin molecule. Similarly, the amine-modified resinmolecule may combine with at least .two such monocarboxylated resinmolecules. In some instances as, for example, when derived fromdiethanolarnine or dipropanolamine the amine-modified resin may becombined with as many as 4 monocarboxylated resin units.

Whenthe carboxylated resin contains more than one carboxyl group, forinstance, two carboxyl groups, the same combinations as above indicatedmay take place but in addition there may be formed linear polymers andalso polymers showing crosslinking, at least to some modest degree.Modest cross-linking is not objectionable provided the resultant productis still soluble in an organic solvent and is thermoplastic. Theobjective is to obtain a product which, regardless of its other uses, isreadily susceptible to oxyalkylation. Thus, soluble complicated resinshave been obtained using dicarboxylated resins and compounds obtainedfrom dialkanolarnines, in which structures other than linear polymerstructure appears.

Returning to the over-simplified presentation of the amine-modifiedresin and particularly one obtained from diethanolamine, for example, orfor that matter from ethylethanolamine, the product would be illustratedthus:

in which R is alkyl or alkanol.

There has been presented earlier an idealized formula for thecarboxylated resin. The terminal part of the molecule may be shown thus:

Without attempting to include all ramifications and particularly wherethe amine radical is polyhydroxylated, it becomes apparent that in theuse of a simple monohydroxylated amine such as ethylethanolamine, in themanufacture of the amine-modified resin, the radical which has beenshown previously becomes part of an ester linkage which may beillustrated thus:

H /C1H4O H H GOO-g1 The compounds can be prepared without the use of anysolvent although for obvious reasons it is preferable that a solvent beused. Indeed, it is specified that the resins employed bexylene-soluble. In every instance xylene was used as a solvent butobviously any other comparable solvent such as ethylbenzene, cymene, orthe like, can be employed. However, xylene seems to be very suitable.

The general procedure was to dissolve the carboxylated resin in xyleneas indicated and then add the aminemodified resin using a refluxcondenser with a phaseseparating trap. The reaction was conducted for aperiod of time at a comparatively low temperature, for instancesomewhere above the boiling point of water, and then gradually was takento a higher temperature, for instance, 140 C. to 150 C. There were tworeasons for this procedure. An effort was made to limit the reaction asfar as possible to the acylation (esterification) and to avoid morecomplicated reactions such as possible ring formation and the like.Secondly, the effort was made in all instances to avoid gelation orcr0ss-linking so as to yield an insoluble product. If the resultant ofreaction became thick and showed incipient cross-linking thereaction wasstopped provided the theoretical amount of water, or approximately thetheoretical amount, had been eliminated. If there happened to be nodanger of. cross-linking or ring formation in light of the particularreactants selected, any suitable temperature could be employed.

Water of reaction as formed was eliminated by means of thephase-separating trap and if required the xylene.

or other solvent employed was eliminated so as to raise the temperaturesufliciently high to eliminate the theoreti-" cal water ofesterification or approximately this amount.

It is not necessary that esterification eliminate all carboxyl radicalsor all hydroxyl radicals. Thus, in the use of a carboxylated resinhaving 2 or more carboxyl radicals if desired the reaction may beconducted so that only one carboxyl radical is reacted. product may havea free carboxyl radical, or a free carboxyl radical and a free hydroxylradical. In such instances where all the carboxyl radicals areesterified there may be free hydroxyl radicals, or even where only onecarboxyl group is reacted.

The entire procedure is conventional and, in fact, has

been described in the formation of other esters of esterih fied productsusing carboxylated resins.

Example 10 The carboxylated resin employed was 4aa. The aminemodifiedresin employed was lb. The molecular weight of carboxylated resin 4amwas 846. A gram mole of the resin, to wit, 846 grams, were reacted with1120 grams of the amine-modified resin (xylenefree basis). The amount ofxylene present both as a solvent for the two reactants and as addedsolvent was 983 grams. The mixture started to reflux at approximately108 C. and

rose rapidly to about C. Xylene was then with TABLE III Wt. of amineOarboxyl- Amt. Amine modified Solvent Max. Ex ated M01. M01. wt. used,modified resin (xylene) Time, temp., Water N o resin ratio grams resin(xyleneat start, hrs. C. out, ml.

Ex. No. free grams basis),

grams Thus, the residual 6006:1360 taut) HHHF- I- I- bSl- OJH H H Notethat in the .last six examples .a mole of dicarboxylated resin wasreacted mole-for-mole with a polyhydroxylated amine-modified resin. Thereaction was continued in an effort to produce a linear polymer, to wit,to esterif y both carboxyls of the carboxylated resin. The reactionprobably ended with free hydroxyl groups and perhaps a structure morecomplicated, at least to some degree than a simple linear polymer. Notethe ratio for example of reactants in 200 is identical with that in butin 200 the amount of water eliminated was approximately 36 grams ascompared with 18 grams in 10.

PART 6 The products obtained as described may be used for variouspurposes in which surface-active agents may be employed. When combinedwith acids such as hydroxy acid, lactic acid, gluconic acid, or thelike, the salts show increased hydrophile properties. When combined withhigher fatty acids, high molal monosul'fonic acids such as mahoganyacids, the products show increased hydrophobe eifect. These compounds assuch, or in salt form, may be employed as additives to demulsifyingagents.

The products are particularly valuable as additives for demulsifyingagents employed in conjunction with concentrated hydrochloric acid. Theymay be used as corrosion inhibitors or rust preventives, particularly incombination with chromium compounds as described in U. S. Patent No.2,450,807, dated October 5, 1948, to Mc- Carthy.

They may be used as anti-stripping agents in connection with asphalt.

In some instances they are effective for the resolution of petroleumemulsions of the oil-in-water type.

The most important use, however, as far as I am aware, is as anintermediate.

The above products can be subjected to oxyalkylation, particularly withan alkylene oxide having not over 4 carbon atoms such as ethylene oxide,butylene oxide, propylene oxide, glycide, methylglycide, etc., toproduce a variety of materials, some of which are extremely hydrophile,others which show hydrophile-hydrophobe balance, particularly ifethylene oxide is used in combination with butylene oxide or propyleneoxide. The compounds so obtained are extremely useful for the resolutionof petroleum emulsions of the water-in-oil type. All that is required isto follow the procedure set forth in U. S. Patent No. 2,636,038, datedApril 21, 1953, to Brandner.

The compounds herein described can be reacted with diepoxides so as toform a more complex molecule and then reacted with monoepoxides as abovedescribed to give additional products useful for various purposes andparticularly the resolution of petroleum emulsions of the water-in-oiltype.

Having thus described my invention what I claim as new and desire tosecure by Letters Patent is 1. An esterification process comprisingreacting (A) a carboxylated phenol-aldehyde resin, and (B) anaminemodified phenol-aldehyde resin in a molar ratio of carboxylatedresin to amine-modified resin of 1 to 4:1; said carboxylated resin (A)being a fusible, carboxyl-containing, xylene-soluble, water-insoluble,low-stage phenolaldehyde resin; said resin being derived by reactionbetween a mixture of a difunctional monohydric hydrocarbon-substitutedphenol and salicylic acid on the one hand, and an aldehyde having notover 8 carbon atoms and having one functional group reactive toward bothcomponents of the mixture on the other hand; the amount of salicylicacid employed in relation to the non-carboxylated phenol beingsuflicient to contribute at least one salicylic acid radical per resinmolecule and the amount of difunctional monohydrichydrocarbon-substituted phenol being sufiicient to contribute at leastone difunctional monohydric hydrocarbon-substituted phenol radical permolecule; said esin being formed in the substantial absence of phenols22 of functionality greater than two, and said phenol being'of theformula in which R is a hydrocarbon radical having at least 4 and notmore than 14 carbon atoms and substituted in one of the positions orthoand para; said amine-modified phenol-aldehyde resin (B) being theproduct obtained by the process of condensing (a) anoxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over v8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of phenols of functionalitygreater than 2; said phenol being of the formula in which R is analiphatic hydrocarbon radical having at least 4 and not more than 24carbon atoms and substituted in the 2, 4, 6 position; (b) a basichydroxylated secondary monoamine having not more than 32 carbon atoms inany group attached to the amino nitrogen atom, and (0) formaldehyde;said condensation reaction being conducted at a temperature suflicientlyhigh to eliminate water and below the pyrolytic point of the reactantsand resultants of reaction; with the further proviso that the molarratio of reactants (c) (b) and (a) be 2, 2 and approximately 1,respectively; and with the further proviso that the resinouscondensation product resulting from the process be heat-stable,oxyalkylation-susceptible and contain at least two alkanol radicals; andwith the final proviso that the product of esterification bethermoplastic and organic solvent-soluble.

2. The process of claim 1 with the proviso that the carboxylated resinmolecule have approximately 5 phenolic nuclei of which not over 2 areobtained from salicylic acid.

3. The process of claim 1 with the proviso that the carboxylated resinmolecule have aproximately 5 phenolic nuclei of which 2 are obtainedfrom salicylic acid.

4. The process of claim 1 with the proviso that the carboxylated resinmolecule have approximately 5 phenolic nuclei of which 2 are obtainedfrom salicylic acid and with the further proviso that the molal ratio ofamine-modified resin to carboxylated resin be 1 to 1.

5. The process of claim 1 with the proviso that the carboxylated resinmolecule have approximately 5 phenolic nuclei of which 2 are obtainedfrom scalicylic acid and with the further proviso that the molal ratioof aminemodified resin to carboxylated resin be 1 to l, and saidamine-modified phenol-aldehyde resin condensate be obtained from adialkanolamine.

6. The process of claim 1 with the proviso that the carboxylated resinmolecule have approximately 5 phenolic nuclei of which 2 are obtainedfrom salicylic acid and with the further proviso that the molal ratio ofaminemodified resin to carboxylated resin be 1 to l, and saidamine-modified phenol-aldehyde resin condensate be obtained from adialkanolamine having not over 6 carbon atoms in the alkanol group.

7. The process of claim 1 with the proviso that the carboxylated resinmolecule have approximately 5 phenolic nuclei of which 2 are obtainedfrom salicylic acid 3.3 and with the further proviso that the molalratio of aminemodified resin to carboxylated resin be 1 to 1, and saidamine-modified resin be obtained by use of diethanolamine as a reactant.

8. The process of claim 1 with the proviso that the carboxylated resinmolecule have approximately 5 phenolic nuclei of which 2 are obtainedfrom salicylic acid and with the further proviso that the molal ratio ofaminemodified resin to carboxylated resin be 1 to 1, and saidamine-modified resin be obtained by use of dipropanoli amine as areactant.

9. The process of claim 1 with the proviso that the carboxylated resinmolecule have approximately 5 phenolic nuclei of which 2 are obtainedfrom salicylic acid and with the further proviso that the molal ratio ofaminemodified resin to carboxylated resin be 1 to 1, and saidamine-modified resin be obtained by use of dibutanolamine as a reactant.I

i 10. The process of claim 1 with the proviso that the carboxylatedresin molecule have approximately 5 phenolic nuclei of which 2 areobtained from salicylic acid and with the further proviso that the molalratio of aminemodified resin to carboxylated resin be 1 to 1, and saidamine-modified resin be obtained by use of dihexanolamine as a reactant.

11. The product obtained by the manufacturing process defined in claim1.

12. The product obtained by the manufacturing process defined in claim2.

13. The product obtained by the manufacturing process defined in claim3.

14. The product obtained by the manufacturing process defined in claim4.

15. The product obtained by the manufacturing process defined in claim5.

16. The product obtained by the manufacturing process defined in claim6.

17. The product obtained by the manufacturing process defined in claim7.

18. The product obtained by the manufacturing process defined in claim8.

19. The product obtained by the manufacturing process defined in claim9.

20. The product obtained by the manufacturing process defined in claim10.

No references cited.

1. AN ESTERIFICATION PROCESS COMPRISING REACTING (A) A CARBOXYLATEDPHENOL-ALDEHYDE RESIN, AND (B) AN AMINEMODIFIED PHENOL-ALDEHYDE RESIN INA MOLAR RATIO OF CARBOXYLATED RESIN TO AMINE-MODIFIED RESIN OF 1 TO 4:1;SAID CARBOXYLATED RESIN (A) BEING A FUSIBLE CARBOXYL-CONTAINING,XYLENE-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN; SAIDRESIN BEING DERIVED BY REACTION BETWEEN A MIXTURE OF A DIFUNCTIONALMONOHYDRIC HYDROCARBON-SUBSTITUTED PHENOL AND SALICYLIC ACID ON THE ONEHAND, AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONEFUNCTIONAL GROUP REACTIVE TOWARD BOTH COMPONENTS OF THE MIXTURE ON THEOTHER HAND; THE AMOUNT OF SALICYLIC ACID EMPLOYED IN RELATION TO THENON-CARBOXYLATED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEAST ONESALICYLIC ACID RADICAL PER RESIN MOLECULE AND THE AMOUNT OF DIFUNCTIONALMONOHYDRIC HYDROCARBON-SUBSTITUTED PHENOL BEING SUFFICIENT TO CONTRIBUTEAT LEAST ONE DIFUNCTIONAL MONOHYDRIC HYDROCARBON-SUBSTITUTED PHENOLRADICAL PER MOLECULE; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCEOF PHENOLS OF FUNCTIONALITY GREATER THAN TWO, AND SAID PHENOL BEING OFTHE FORMULA